在N_2中[V_nCr_(3-n)(μ_3-O)(μ-O_2CCH_3)_6(THF)_3]X[n=0-3,X=Cl^-,ClO_4^-,(VO_5)_(0.5)^-]及[V_nFe_(3-n)(μ_3O)(μ-O_2CCH_3)_6(THF)_3]X(n=0-3,X=Cl^-)反应行为的原位红外光谱研究

In Situ IR Study of the Reaction Behavior of Clusters [V_nCr_(3-n)(μ_3-O)(μ-O_2CCH_3)_6(THF)_3]X[n=0-3,X=Cl^-,ClO_4^-,(VO_5)_(0.5)^-] and [V_nFe_(3-n)(μ_3-O)(μ-O_2CCH_3)_6(THF)_3]X(n=0-3,X=Cl^-) in Nitrogen Atomsphere

利用原位红外光谱研究标题化合物在N2 中的反应行为。发现它们在不同温度下能使乙酸分别转化为丙酮和甲烷。它们对乙酸的丙酮化反应活性顺序 :[V3OAT]>[VFe2 OAT],[V2 CrOAT]>[Fe3OAT],[VCr2 OAT]>[Cr3OAT][OAT =(μ3 O) (μ O2 CCH3) 6(THF) 3]。它们对乙酸的甲烷化反应活性顺序 :[Cr3OAT]>[VCr2 OAT],[V2 CrOAT]>[V3OAT]>[VFe2 OAT],[FeO3OAT]。对乙酸的丙酮化反应活性[Fe3OAT]明显低于 [Fe3OAH][OAH =(μ3 O) (μ O2 CCH3) 6(H2 O) 3]。对乙酸的甲烷化反应活性 [Cr3OAT]也明显低于 [CrOAH]。并对上述 [Fe3OAT],[Cr3OAT]与 [Fe3OAH],[Cr3OAH]之间差异进行了讨论。

The reaction behavior of the title complexes have been investigated by means of in situ IR in nitrogen atmosphere.It has been found that they enabled the acetic acid to convert to acetone and methane in different temperatures.The results indicate that the sequence of the ketonization reaction activity for the clusters was [V 3OAT]>[VFe 2OAT],[V 2CrOAT]>[Fe 3OAT],[VCr 2OAT]>[Cr 3OAT][OAT=(μ 3-O)(μ-O 2CCH 3) 6(THF) 3],and the sequence of the methanation reaction activity for the clusters was [Cr 3OAT]>[VCr 2OAT],[V 2CrOAT]>[V 3OAT]>[VFe 2OAT],[Fe 3OAH].The ketonization reaction activity of [Fe 3OAT] were obviously lower than that of [Fe 3OAH][OAH=(μ 3-O)(μ-O 2CCH 3) 6(H 2O) 3] and the methanation reaction activity of [Cr 3OAT] were also much lower than that of [Cr 3OAH].The difference between [Fe 3OAH],[Cr 3OAT] and [Fe 3OAH],[Cr 3OAH] metioned above were discussed.